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Projeto de investigação
Synthesis of new homooxacalixarene based anion receptors
Financiador
Autores
Publicações
Bidentate Urea Derivatives of p-tert-Butyldihomooxacalix[4]arene: Neutral Receptors for Anion Complexation
Publication . Marcos, Paula M.; Teixeira, Filipa A.; Segurado, Manuel A. P.; Ascenso, José R.; Bernardino, Raul J.; Michel, Sylvia; Hubscher-Bruder, Véronique
Three new bidentate ureidodihomooxacalix[4]- arene derivatives (phenyl 5a, n-propyl 5b, and tert-butyl 5c) were synthesized in four steps from the parent compound ptert- butyldihomooxacalix[4]arene and obtained in the cone conformation, as shown by NMR studies. The binding ability of these neutral receptors toward spherical, linear, trigonal planar, and tetrahedrical anions was assessed by 1H NMR and UV-vis titrations. The structures and complexation energies of some complexes were also studied by DFT methods. The data showed that the association constants are strongly dependent on the nature of the substituent (aryl/alkyl) at the urea moiety. In general, for all the receptors, the association constants decrease with decrease of anion basicity. Ph-urea 5a is the best anion receptor, showing the strongest complexation for F- (log Kassoc = 3.10 in CDCl3) and also high binding affinity for the carboxylates AcO- and BzO-. Similar results were obtained by UV-vis studies and were also corroborated by DFT calculations.
Synthesis and anion binding properties of new dihomooxacalix[4]arene diurea and dithiourea receptors
Publication . Marcos, Paula M.; Teixeira, Filipa A.; Segurado, Manuel A. P.; Ascenso, José R.; Bernardino, Raul J.; Brancatelli, Giovanna; Geremia, Silvano
Functionalization of the lower rim of p-tert-butyldihomooxacalix[4]arene with two (thio)ureido moieties provided new diurea (n-propyl 5a, tert-butyl 5b and phenyl 5c) and dithiourea (phenyl 5d) derivatives, all in the cone conformation, as shown by NMR studies. The X-ray crystal structure of 5c is reported. The binding ability of these neutral receptors towards a large variety of anions was assessed by 1H NMR titrations. The structures and complexation energies of some complexes were also studied using DFT methods. The data showed that, in general, the association constants decrease with decrease of anion basicity and they are strongly dependent on the nature of the substituent at the urea moiety. Phenyl-(thio)urea derivatives 5c and 5d are the best anion receptors, showing the strongest complexation for F− (log Kass=2.70 and 2.75, respectively) and also for the oxoanions AcO−, BzO− and H2 PO4. These results were corroborated by DFT calculations.
Unidades organizacionais
Descrição
Palavras-chave
Calixarenes, Receptors, Hydrogen bonds, Anions, Exact sciences ,Exact sciences/Chemical sciences
Contribuidores
Financiadores
Entidade financiadora
Fundação para a Ciência e a Tecnologia, I.P.
Programa de financiamento
Concurso para Projectos de I&D em todos os Domínios Científicos - 2006
Número da atribuição
PTDC/QUI/69858/2006